CN105442100B - Superhigh molecular weight polyethylene fibers and preparation method thereof - Google Patents
Superhigh molecular weight polyethylene fibers and preparation method thereof Download PDFInfo
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- CN105442100B CN105442100B CN201511022257.8A CN201511022257A CN105442100B CN 105442100 B CN105442100 B CN 105442100B CN 201511022257 A CN201511022257 A CN 201511022257A CN 105442100 B CN105442100 B CN 105442100B
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- molecular weight
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
- D01F11/04—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers
- D01F11/06—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02J—FINISHING OR DRESSING OF FILAMENTS, YARNS, THREADS, CORDS, ROPES OR THE LIKE
- D02J1/00—Modifying the structure or properties resulting from a particular structure; Modifying, retaining, or restoring the physical form or cross-sectional shape, e.g. by use of dies or squeeze rollers
- D02J1/22—Stretching or tensioning, shrinking or relaxing, e.g. by use of overfeed and underfeed apparatus, or preventing stretch
- D02J1/222—Stretching in a gaseous atmosphere or in a fluid bed
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- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02J—FINISHING OR DRESSING OF FILAMENTS, YARNS, THREADS, CORDS, ROPES OR THE LIKE
- D02J13/00—Heating or cooling the yarn, thread, cord, rope, or the like, not specific to any one of the processes provided for in this subclass
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Artificial Filaments (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
Include that the ultra-high molecular weight polyethylene spun filament after extractant is placed in the modified solution containing the quick crosslinking agent of spoke to carry out impregnation the invention discloses a kind of superhigh molecular weight polyethylene fibers and preparation method thereof；Spun filament after the dipping passes through drying, Multi-stage heat air draft；Using the fiber after drawing-off described in high-energy ray irradiation, to obtain irradiated crosslinked superhigh molecular weight polyethylene fibers.The preparation method of superhigh molecular weight polyethylene fibers provided by the invention is by introducing the quick crosslinking agent of spoke in the ultra-high molecular weight polyethylene spun filament after extractant, the quick crosslinking agent of spoke is set easily to enter fibrous inside, between drawing process is embedded in fiber macromolecular, and superhigh molecular weight polyethylene fibers crosslinking is caused by the irradiation of high-energy ray, therefore, the process of the present invention is simple, easy to operate, and thus obtained superhigh molecular weight polyethylene fibers have high intensity, the performance of low creep.
Description
Technical field
The present invention relates to technical field of polymer materials, and in particular to a kind of superhigh molecular weight polyethylene fibers and its preparation
Method.
Background technology
Superhigh molecular weight polyethylene fibers, density ratio water is small, is a kind of currently the only height that can be swum on the water surface
Performance fibers have excellent mechanical property.Its backbone structure is good, has very high specific strength, under phase homogenous quantities, intensity
It is 15 times of steel wire rope, 10 times of ordinary chemical fiber and high-quality steel, it is higher than aramid fiber by 40%, it is only second to superfine carbon fiber, and resistance to
Photosensitiveness is good, exposes 1 year or more its intensity outdoors and is slightly decreased.Superhigh molecular weight polyethylene fibers have high intensity, high-modulus,
Preferable wearability, weatherability and corrosion resistance, are widely used in shellproof protective articles, naval vessels windsurfing, sports equipment, rope
The sea stores such as rope and hawser and fishing net.
But superhigh molecular weight polyethylene fibers macromolecular main chain is made of methylene, unprotected side chain, molecule does not have polarity,
Only have van der Waals interaction, intermolecular force low between strand.In load bearing process, between strand and between chip
Easy to produce Relative sliding, cause size, form it is unstable, macroscopically showing as larger creep, limiting it in state
Application in people economic field.Therefore, croop property is improved using method, to the further hair of superhigh molecular weight polyethylene fibers
Exhibition and application have the important meaning.
Japan Patent JP6208111, international monopoly WO2009043598 and application number CN200880110448.1,
The patent of invention of CN200880110402.X, CN201210327505.X, CN201280029173.5 are described from molecular structure
Setting out improves the method for fibres show creep, and the raw material of selection is that the superhigh molecular weight polyethylene fibers with extremely low branched structure are former
Material, the degree of branching are that every 100 or 1000 carbon atoms include the short chain groups such as 2 methyl side groups below or ethyl, butyl.But
It is that branching molecule chain is fettered in drawing process in this method, influences the final drafting multiple of fiber, and then influence fiber
Fracture strength.
The patent of invention of application number CN200910162583.7, CN201110271729.9, CN201310471406.3 are situated between
Continued improve superhigh molecular weight polyethylene fibers creep resistance method, in spinning process add inorganic nanometer powder (such as
Nanometer inorganic composite materials, carbon nanotube, graphene powder, SiO2), score is made by the physical crosslinking point of inorganic nanoparticles
It is crosslinked between son, to improve the creep-resistant property of fiber.But the addition of inorganic nanoparticles can make supra polymer
Weight polyethylene fiber spinnability is deteriorated, and then influences the mechanical property of fiber.
Invention content
In view of this, it is an object of the invention to propose superhigh molecular weight polyethylene fibers and preparation method thereof, to improve
Its creep-resistant property.
Based on above-mentioned purpose, the preparation method of superhigh molecular weight polyethylene fibers provided by the invention includes the following steps：
By the ultra-high molecular weight polyethylene spun filament after extractant be placed in the modified solution containing the quick crosslinking agent of spoke into
Row impregnation；
Spun filament after the dipping passes through drying, Multi-stage heat air draft；
Using the spun filament after drawing-off described in high-energy ray irradiation, to obtain irradiated crosslinked superhigh molecular weight polyethylene
Alkene fiber.
In some embodiments of the invention, the high-energy ray is electron beam or gamma ray.
In some embodiments of the invention, the step of spun filament using after drawing-off described in high-energy ray irradiation is
It is carried out in vacuum, nitrogen, argon gas or acetylene gas, the irradiation dose of the high-energy ray is 1~500kGy.
In some embodiments of the invention, the modified solution and ultra-high molecular weight polyethylene containing the quick crosslinking agent of spoke
The mass ratio of spun filament is 5:1~50:1.
In some embodiments of the invention, it is different to be selected from triallyl cyanurate, triallyl for the quick crosslinking agent of the spoke
Cyanurate, trimethylolpropane trimethacrylate, 1,6 hexanediol diacrylate, tri (propylene glycol) diacrylate
At least one of with double pentaerythritol methacrylate.
In some embodiments of the invention, the solvent of the modified solution is selected from acetone, ethyl alcohol, tetrahydrofuran, positive heptan
At least one of alkane and gasoline.
In some embodiments of the invention, in the modified solution the quick crosslinking agent of spoke mass percentage be 1~
10%.
In some embodiments of the invention, the spun filament after the dipping is spontaneously dried at room temperature.
In some embodiments of the invention, the Multi-stage heat air draft be in 70~140 DEG C of hot-air into
3~5 grades of drawing-offs of row, drafting multiple are 10~40 times.
The present invention also provides a kind of superhigh molecular weight polyethylene fibers, the superhigh molecular weight polyethylene fibers are according to above-mentioned
The preparation method of superhigh molecular weight polyethylene fibers is prepared.
From the above it can be seen that the preparation method of superhigh molecular weight polyethylene fibers provided by the invention is by extracting
It takes and introduces the quick crosslinking agent of spoke after solvent in ultra-high molecular weight polyethylene spun filament, the quick crosslinking agent of spoke is made easily to enter fibrous inside,
Between drawing process is embedded in fiber macromolecular, and superhigh molecular weight polyethylene fibers are caused by the irradiation of high-energy ray and are handed over
Connection, therefore, process of the invention is simple, easy to operate, and thus obtained superhigh molecular weight polyethylene fibers have high intensity, low
The performance of creep.
Specific implementation mode
To make the objectives, technical solutions, and advantages of the present invention clearer, below in conjunction with specific embodiment, to this hair
Bright further description.
Embodiment 1
Using acetone as solvent, triallyl cyanurate is dissolved in acetone, it is dense to prepare triallyl cyanurate quality
The acetone soln that degree is 2%.Ultra-high molecular weight polyethylene as-spun fibre after extractant is placed in the acetone soln, is impregnated
The mass ratio of processing 20min, the acetone soln and ultra-high molecular weight polyethylene spun filament is 5:1.
Spun filament is taken out from acetone soln, is spontaneously dried in air, then at 70 DEG C, 100 DEG C, 120 DEG C and 140 DEG C
Hot-air in carry out level Four hot gas spring, total draft multiple be 15 times.
Under nitrogen protection by the fiber after drawing-off, it is irradiated by the electron beam device that dosage rate is 5kGy/s, irradiates agent
Amount is 10kGy, obtains irradiated crosslinked superhigh molecular weight polyethylene fibers.
Embodiment 2
Using tetrahydrofuran as solvent, iso-cyanuric acid triallyl ester is dissolved in tetrahydrofuran, it is different to prepare triallyl
The tetrahydrofuran solution that cyanurate mass concentration is 4%.By the ultra-high molecular weight polyethylene as-spun fibre after extractant
It is placed in the tetrahydrofuran solution, impregnation 30min, the tetrahydrofuran solution and ultra-high molecular weight polyethylene spun filament
Mass ratio is 10:1.
Spun filament is taken out from tetrahydrofuran solution, is spontaneously dried in air, then at 90 DEG C, 110 DEG C and 140 DEG C
Level Four hot gas spring is carried out in hot-air, total draft multiple is 20 times.
By the fiber after drawing-off under acetylene protection, is irradiated by the electron beam device that dosage rate is 5kGy/s, irradiate agent
Amount is 20kGy, obtains irradiated crosslinked superhigh molecular weight polyethylene fibers.
Embodiment 3
Using ethyl alcohol as solvent, 1,6- hexanediyl esters are dissolved in ethyl alcohol, prepare 1,6- hexanediyls
The ethanol solution that ester mass concentration is 6%.It is molten that ultra-high molecular weight polyethylene as-spun fibre after extractant is placed in the ethyl alcohol
In liquid, the mass ratio of impregnation 30min, the ethanol solution and ultra-high molecular weight polyethylene spun filament are 20:1.
Spun filament is taken out from ethanol solution, is spontaneously dried in air, then at 90 DEG C, 110 DEG C, 120 DEG C, 130 DEG C
With progress Pyatyi hot gas spring in 140 DEG C of hot-air, total draft multiple is 24 times.
Under vacuum by the fiber after drawing-off, it is irradiated by the electron beam device that dosage rate is 10kGy/s, irradiation dose is
40kGy obtains irradiated crosslinked superhigh molecular weight polyethylene fibers.
Embodiment 4
Using n-heptanol as solvent, tri (propylene glycol) diacrylate is dissolved in n-heptanol, prepares tripropylene glycol
The n-heptanol solution that diacrylate mass concentration is 8%.Ultra-high molecular weight polyethylene as-spun fibre after extractant is set
In the n-heptanol solution, impregnation 40min, the mass ratio of the n-heptanol solution and ultra-high molecular weight polyethylene spun filament
It is 30:1.
Spun filament is taken out from n-heptanol solution, is spontaneously dried in air, then at 110 DEG C, 120 DEG C, 130 DEG C and
Level Four hot gas spring is carried out in hot-air at 140 DEG C, total draft multiple is 30 times.
Under nitrogen protection by the fiber after drawing-off, pass through the 60Co- gamma-ray irradiations that dosage rate is 3.6kGy/h, irradiation
Dosage is 60kGy, obtains irradiated crosslinked superhigh molecular weight polyethylene fibers.
Embodiment 5
Using acetone as solvent, double pentaerythritol methacrylate is dissolved in acetone, prepares six acrylic acid of dipentaerythritol
The acetone soln that ester mass concentration is 10%.It is molten that ultra-high molecular weight polyethylene as-spun fibre after extractant is placed in the acetone
In liquid, the mass ratio of impregnation 60min, the acetone soln and ultra-high molecular weight polyethylene spun filament are 40:1.
Spun filament is taken out from acetone soln, is spontaneously dried in air, then at 120 DEG C, 130 DEG C, 140 DEG C and 140
Level Four hot gas spring is carried out in hot-air at DEG C, total draft multiple is 26 times.
Under nitrogen protection by the fiber after drawing-off, it is irradiated by the electron beam device that dosage rate is 20kGy/s, irradiates agent
Amount is 80kGy, obtains irradiated crosslinked superhigh molecular weight polyethylene fibers.
Creep-resistant property is tested
Creep elongation test condition：Under the conditions of 20 ± 2 DEG C of temperature, relative humidity 63 ± 3%, application stress is fiber
The 50% of ultimate strength, creep time 60min.
It is as a result as follows by the performance comparison of superhigh molecular weight polyethylene fibers and untreatment fiber made from embodiment 1-5
Shown in table：
Number 0 is to handle (without dipping, stretching and radiation treatment, only to pass through normal stretch without the method for the present invention
Technique) superhigh molecular weight polyethylene fibers.
As can be seen from the table, superhigh molecular weight polyethylene fibers have made from the preparation method provided through the invention
Preferable creep-resistant property, while the superhigh molecular weight polyethylene fibers still maintain higher intensity.
Ultra-high molecular weight polyethylene spun filament aggregated structure is loose after extractant, unformed area is more, this hair
The preparation method of the superhigh molecular weight polyethylene fibers of bright offer passes through the ultra-high molecular weight polyethylene spun filament after extractant
The quick crosslinking agent of middle introducing spoke makes the quick crosslinking agent of spoke easily enter fibrous inside, between drawing process is embedded in fiber macromolecular, and
Cause superhigh molecular weight polyethylene fibers crosslinking by the irradiation of high-energy ray, therefore, process of the invention is simple, operation side
Just, thus obtained superhigh molecular weight polyethylene fibers have high intensity, the performance of low creep.
It can be seen that main advantage in the present invention：
(1) the ultra-high molecular weight polyethylene as-spun fibre after extractant, crystalline orientation degree is low, and aggregated structure is loose,
The quick crosslinking agent of spoke easily enters fibrous inside, and cross-linking radiation degree is higher, and process of the present invention is simple, easy to operate；
(2) the quick crosslinking agent of spoke penetrates into fibrous inside, in drawing process together with fiber macromolecular orientations, to fibre
The tensile property of dimension does not influence substantially, and can directly be carried out using existing ultra-high molecular weight polyethylene production line, nothing
Scrap build expense；
(3) this method causes crosslinking technological using ionising radiation, environmental-friendly, simple for process, quick, production cost is low.
Those of ordinary skills in the art should understand that：The discussion of any of the above embodiment is exemplary only, not
It is intended to imply that the scope of the present disclosure (including claim) is limited to these examples；Under the thinking of the present invention, above example
Or can also be combined between the technical characteristic in different embodiments, step can be realized with random order, and be existed such as
Many other variations of the different aspect of the upper present invention, for simplicity, they are not provided in details.Therefore, it is all
Within the spirit and principles in the present invention, any omission, modification, equivalent replacement, improvement for being made etc. should be included in the present invention's
Within protection domain.
Claims (4)
1. a kind of preparation method of superhigh molecular weight polyethylene fibers, which is characterized in that include the following steps：
Ultra-high molecular weight polyethylene spun filament after extractant is placed in the modified solution that mass concentration is 4% and is impregnated
30min is handled, the wherein solute in modified solution is the quick crosslinking agent of iso-cyanuric acid triallyl ester spoke, molten in modified solution
Agent is tetrahydrofuran；
Spun filament after the dipping passes through drying, Multi-stage heat air draft；
Using the fiber after drawing-off described in electron beam high-energy ray irradiation, to obtain irradiated crosslinked superhigh molecular weight polyethylene
Alkene fiber；
Wherein, the step of fiber using after drawing-off described in electron beam irradiation is carried out in acetylene gas, and the high energy is penetrated
The irradiation dose of line is 20kGy；
The modified solution containing iso-cyanuric acid triallyl ester and the mass ratio of ultra-high molecular weight polyethylene spun filament are
10:1。
2. the preparation method of superhigh molecular weight polyethylene fibers according to claim 1, which is characterized in that after the dipping
Spun filament spontaneously dried at room temperature.
3. the preparation method of superhigh molecular weight polyethylene fibers according to claim 1, which is characterized in that the multistage
Hot-air drawing-off is 3~5 grades of drawing-offs of progress in 70~140 DEG C of hot-air, and total draft multiple is 10~40 times.
4. a kind of superhigh molecular weight polyethylene fibers, which is characterized in that the superhigh molecular weight polyethylene fibers are wanted according to right
The preparation method of the superhigh molecular weight polyethylene fibers described in any one of 1~3 is asked to be prepared.
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| CN201511022257.8A CN105442100B (en) | 2015-12-29 | 2015-12-29 | Superhigh molecular weight polyethylene fibers and preparation method thereof |
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| CN201511022257.8A CN105442100B (en) | 2015-12-29 | 2015-12-29 | Superhigh molecular weight polyethylene fibers and preparation method thereof |
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| CN107974827B (en) * | 2016-10-21 | 2021-02-05 | 中国石油化工股份有限公司 | Anti-dripping fiber and preparation method and product thereof |
| CN106676879B (en) * | 2016-12-30 | 2019-04-26 | 湖南中泰特种装备有限责任公司 | Surface modification of super-high molecular-weight polyethylene fiber surface solution, preparation method, modified with ultrahigh molecular weight polyethylene fiber and method of modifying |
| CN107938159A (en) * | 2017-12-18 | 2018-04-20 | 太和县双飞绳业有限公司 | A kind of preparation method of acid and alkali-resistance polyethylene fibre netting |
| CN114592344B (en) * | 2022-03-29 | 2024-04-16 | 武汉纺织大学 | Preparation method of high-strength high-toughness fiber material |
| CN115928258B (en) * | 2022-12-28 | 2023-11-03 | 盐城优和博新材料有限公司 | Coarse monofilament modified ultra-high molecular weight polyethylene fiber and preparation method thereof |
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Denomination of invention: Ultra high molecular weight polyethylene fiber and its preparation method Effective date of registration: 20201217 Granted publication date: 20180907 Pledgee: Hunan Linli rural commercial bank Limited by Share Ltd. Pledgor: Hunan Zhongtal Special Equipment Co.,Ltd. Registration number: Y2020430000043 |
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